JP6186286B2 - Method for producing laminate for acid gas separation, laminate for acid gas separation, and acid gas separation module - Google Patents

Description

  The present invention relates to a method for producing an acid gas separation laminate that selectively separates an acid gas from a raw material gas, an acid gas separation laminate, and an acid gas separation module.

  In recent years, development of a technique for selectively separating an acidic gas such as carbon dioxide from a raw material gas (a gas to be treated) has been advanced. For example, an acid gas separation membrane that separates an acid gas from a raw material gas using an acid gas separation membrane that selectively permeates the acid gas has been developed.

For example, in Patent Document 1, a multilayer body including an acidic gas separation membrane is wound around a central cylinder (a central permeate collecting pipe) for collecting separated acidic gas, in which through holes are formed in a tube wall. An acid gas separation module is described.
The acidic gas separation module disclosed in Patent Document 1 uses a so-called dissolution diffusion membrane as the acidic gas separation membrane. The dissolution diffusion membrane separates the acid gas from the raw material gas by utilizing the difference in solubility between the acidic gas and the substance to be separated in the membrane and the diffusivity in the membrane.

Patent Document 2 discloses an aqueous solution containing a carbon dioxide carrier on a carbon dioxide permeable support as an acidic gas separation membrane (carbon dioxide separation gel membrane) for separating carbon dioxide (carbon dioxide) from a raw material gas. Describes an acid gas separation membrane in which a hydrogel membrane is formed by absorbing a bisphenol into a vinyl alcohol-acrylate copolymer having a crosslinked structure.
This acid gas separation membrane is an acid gas separation membrane using a so-called facilitated transport membrane. The facilitated transport film has a carrier that reacts with an acidic gas such as a carbon dioxide carrier in the film, and the acidic gas is separated from the source gas by transporting the acidic gas to the opposite side of the film with this carrier.

  Such an acid gas separation membrane is usually formed on the surface of a gas-permeable support (porous support) such as a non-woven fabric or a porous membrane on the surface of the above-mentioned dissolution diffusion membrane and facilitated transport membrane (hereinafter referred to as both). And a separation layer).

Therefore, when the acid gas separation membrane is used, the separation layer may gradually enter (penetrate) the porous support. In particular, the facilitated transport film is often a gel film or a low-viscosity film in order to move or transport acidic gas. Therefore, when the acidic gas separation membrane using the facilitated transport membrane is used, the separation layer gradually enters the porous support.
In the acidic gas separation membrane, the separation ability of the acidic gas decreases with time due to the separation layer entering the porous support.
In addition, the facilitated transport film needs to retain a large amount of moisture in the film in order to sufficiently function the carrier. Therefore, a polymer having extremely high water absorption and water retention is used for the facilitated transport film. In addition, in the facilitated transport membrane, as the content of a carrier such as a metal carbonate increases, the water absorption increases and the separation performance of the acid gas improves. That is, the facilitated transport film is often a very soft (low viscosity), gel film.
In addition, in an acidic gas separation membrane using a facilitated transport membrane, a raw material gas having a temperature of 100 to 130 ° C. and a humidity of about 90% is supplied at a pressure of about 1.5 MPa when the acidic gas is separated.
Therefore, in an acidic gas separation membrane using a facilitated transport membrane, the facilitated transport membrane tends to enter the porous support and has low durability.

On the other hand, in Patent Document 3, a solution containing a polymer as a main component is applied to the surface of a porous support to form a base layer made of a breathable polymer such as a silicon-based polymer. Above, there is described a method for producing an acidic gas separation membrane (a method for producing a thin film) in which a separation layer is formed by applying and drying an organic solvent solution whose main component is a material to be a separation layer.
In the acidic gas separation membrane by this production method, by having an underlayer made of a polymer having air permeability, a uniform separation layer can be formed, and a low viscosity separation layer can be prevented from entering the porous support.

Japanese Patent Laid-Open No. 4-215824 Japanese Patent Publication No. 7-102310 JP-A-62-140620

  As shown in Patent Document 3, a porous support is formed by forming a non-porous underlayer having air permeability such as a silicone-based polymer on the surface of the porous support and forming a separation layer thereon. The separation layer can be prevented from entering.

  However, if the coating liquid for the facilitated transport film is applied onto a smooth silicone polymer that is hydrophobic, the coating liquid will be repelled, resulting in uneven film thickness and formation of pores. There is a possibility that a simple facilitated transport film cannot be formed. In addition, the formed facilitated transport film retains a large amount of moisture in the film, and thus has low adhesion to a hydrophobic silicone polymer. Therefore, there is a problem that the facilitated transport film is easily peeled off and the durability is low.

  An object of the present invention is to solve such problems of the prior art, and the acid gas separation layer can be prevented from entering the porous support, and the coating solution for the acid gas separation layer can be repelled. And a method for producing an acidic gas separation laminate capable of suitably producing a highly durable acidic gas separation layer by improving adhesion between the silicone resin layer and the acidic gas separation layer, and for acidic gas separation It is to provide a laminate and a separation module.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have a separation layer forming step of forming an acidic gas separation layer on the silicone resin layer of the composite, and a composite provided for the separation layer forming step When the ratio of the protrusions on the surface of the silicone resin layer is 0.1 / μm ² to 50 / μm ² , the acidic gas separation layer can be prevented from entering the porous support, and the facilitated transport film The present invention has been completed by finding that a highly durable acidic gas separation layer can be suitably produced by preventing the coating liquid from being repelled and improving the adhesion between the silicone resin layer and the acidic gas separation layer. I let you.
That is, this invention provides the manufacturing method of the laminated body for acidic gas separation of the following structures, the laminated body for acidic gas separation, and a separation module.

(1) Acidity including a composite in which a silicone resin layer is provided on at least a part of the surface of the porous support, a carrier that reacts with acidic gas, and a water-absorbing polymer that supports the carrier, which are formed on the silicone resin layer. A method for producing a laminate for acidic gas separation comprising a gas separation layer, comprising a separation layer forming step of forming an acidic gas separation layer on a silicone resin layer of a composite, and provided for the separation layer forming step method for producing a fraction of the protrusions of the surface of the composite of the silicone resin layer is 0.1 or / [mu] m ² to 50 pieces / [mu] m ² at which the acid gas separation laminate.

(2) The manufacturing method of the laminated body for acidic gas separation as described in (1) whose water absorbing polymer is a polyvinyl alcohol polyacrylic acid copolymer.
(3) The manufacturing method of the laminated body for acidic gas separation as described in (1) or (2) in which a carrier contains the compound containing alkali metal carbonate.

(4) The manufacturing method of the laminated body for acidic gas separation in any one of (1)-(3) whose film thickness of a silicone resin layer is 10 micrometers or less.
(5) silicone resin layer, wherein by including a filler, in any of the percentage of the surface of the protrusions is obtained by a 0.1 or / [mu] m ² to 50 pieces ^{/ μm 2 (1) ~ (} 4) Of producing a laminate for acid gas separation.

(6) In the separation layer forming step, the acidic composition according to any one of (1) to (5), in which a coating composition to be an acidic gas separation layer is applied to the surface of the silicone resin layer by a roll-to-roll method. A method for producing a laminate for gas separation.
(7) The manufacturing method of the laminated body for acidic gas separation as described in (6) whose surface tension of a coating composition is 63 mN / m or less.
(8) The manufacturing method of the laminated body for acidic gas separation as described in (6) or (7) whose viscosity of the coating composition in 25 degreeC is 100 cp or more.

(9) An acidic composition comprising a composite provided with a silicone resin layer on at least a part of the surface of the porous support, a carrier that reacts with an acidic gas, and a water-absorbing polymer that supports the carrier, formed on the silicone resin layer. An acid gas separation laminate comprising a gas separation layer, wherein the ratio of protrusions at the interface between the silicone resin layer and the acid gas separation layer is 0.1 / μm ² to 50 / μm ² Laminated body.
(10) An acid gas separation module having the acid gas separation laminate according to (9).

  According to the present invention, the acidic gas separation layer can be prevented from entering the porous support, and the coating liquid for the facilitated transport film can be prevented from being repelled, and the adhesion between the silicone resin layer and the acidic gas separation layer can be prevented. Thus, an acidic gas separation layer having high durability can be suitably produced. Therefore, the laminated body for acidic gas separation which is excellent in durability can be obtained.

It is a figure which shows notionally an example of the laminated body for acidic gas separation manufactured with the manufacturing method of the laminated body for acidic gas separation of this invention. It is a figure which shows notionally an example of the manufacturing apparatus which enforces the manufacturing method of the laminated body for acidic gas separation of this invention. It is a figure which shows notionally an example of the manufacturing apparatus which implements 1 process of another example of the manufacturing method of this invention. It is a figure which shows notionally another example of the manufacturing apparatus which enforces the manufacturing method of this invention. It is a figure which shows notionally an example of the acidic gas separation module using the laminated body for acidic gas separation produced with the manufacturing method of this invention.

  Hereinafter, a method for producing an acid gas separation laminate of the present invention, an acid gas separation laminate produced by the production method, and an acid gas separation module using the acid gas separation laminate will be described with reference to the accompanying drawings. Based on the preferred embodiment shown, it demonstrates in detail.

FIG. 1 shows an acidic gas separation laminate (hereinafter also referred to as “laminate”) produced by the method for producing an acidic gas separation laminate of the present invention (hereinafter also referred to as “the production method of the present invention”). An example is shown conceptually.
This laminated body 10 is obtained by laminating an acidic gas separation layer (facilitated transport membrane) 16 on a composite 18 formed by forming a silicone resin layer 14 on the surface of a porous support 12. As shown in the figure, the acidic gas separation layer 16 is laminated on the surface of the silicone resin layer 14.
In the present invention, the ratio of protrusions at the interface between the silicone resin layer 14 and the acid gas separation layer 16 is 0.1 / μm ² to 50 / μm ² . In the laminate 10 having such an interface roughness, the acidic gas separation layer 16 is formed on the silicone resin layer 14 having a surface protrusion ratio of 0.1 / μm ² to 50 / μm ^2. Is obtained.
The ratio of the protrusions on the surface of the silicone resin layer 14 will be described in detail later.

  As described above, in an acid gas separation laminate using an acid gas separation layer (facilitated transport membrane), the acid gas separation layer, which is a soft gel membrane, penetrates into the porous support (soaks in) and has poor durability. There is a problem. On the other hand, by having the silicone resin layer 14 on the surface of the porous support 12 and forming the acid gas separation layer 16 on the surface of the silicone resin layer 14, the acid gas separation layer 16 is formed into the porous support 12. It can prevent getting into.

However, as described above, the silicone resin layer is hydrophobic and has low adhesion with the acidic gas separation layer that retains a large amount of moisture in the membrane, so that the acidic gas separation layer is easily peeled off and the durability is low. was there. On the other hand, the ratio of the protrusions of the silicone resin layer at the interface between the silicone resin layer 14 and the acid gas separation layer 16 is 0.1 / μm ² to 50 / μm ² , Durability can be increased by improving adhesion with the acidic gas separation layer 16.
The specific configurations of the porous support 12, the silicone resin layer 14, the acidic gas separation layer, and the like will be described in detail later.

Next, the manufacturing method of this invention which manufactures said laminated body 10 for acidic gas separation is demonstrated.
The production method of the present invention includes a separation layer forming step of forming an acidic gas separation layer on the composite 18 in which the silicone resin layer 14 is provided on at least a part of the surface of the porous support 12. The ratio of the protrusions on the surface of the silicone resin layer 14 of the composite 18 subjected to the process is 0.1 / μm ² to 50 / μm ² . In other words, the production method of the present invention is a composite 18 in which the silicone resin layer 14 is applied to at least a part of the surface of the porous support 12, and the ratio of protrusions on the surface of the silicone resin layer 14 is 0.1. preparing a number / [mu] m ² to 50 pieces / [mu] m ² a is complex 18, on the complex 18, is that having a separation layer forming step of forming an acidic gas separation layer.

In FIG. 2, an example of the manufacturing apparatus which implements the manufacturing method of this invention is shown notionally.
The production method of the present invention uses a long composite 18 and applies a coating composition that becomes the acidic gas separation layer 16 on the surface of the composite 18 by a so-called roll-to-roll method (hereinafter also referred to as RtoR). The laminated body 10 for acid gas separation is manufactured by coating and curing.
As is well known, RtoR is a process in which an object to be processed is pulled out from a roll wound with a long object to be processed, and the object to be processed is applied and cured while being conveyed in the longitudinal direction. This is a manufacturing method of winding a processed object in a roll shape.

First, the composite 18 used in the production method of the present invention will be described.
In the production method of the present invention, the composite 18 forming the acidic gas separation layer 16 is obtained by providing the silicone resin layer 14 on at least a part of the surface of the porous support 12.

The porous support body 12 (hereinafter also referred to as the support body 12) is permeable to an acidic gas such as carbon dioxide gas, and has a silicone resin layer 14 formed on the surface, and the surface of the silicone resin layer 14 or The acidic gas separation layer 16 formed on the surface of the support 12 is supported.
As the support 12, various known materials can be used as long as they can exhibit this function.

In the production method of the present invention, the porous support may be a single layer. However, the porous support preferably has a two-layer structure composed of the porous film 12a and the auxiliary support film 12b, like the support 12 shown in FIG. When the support 12 has such a two-layer structure, the above-described acidic gas permeability and the function of supporting the silicone resin layer 14 and the acidic gas separation layer 16 are more reliably expressed.
When the porous support is a single layer, various materials exemplified below as the porous film 12a and the auxiliary support film 12b can be used as the forming material.

In the two-layered support 12, the porous film 12 a is the surface on which the silicone resin layer 14 is formed. An acidic gas separation layer 16 is formed on the surface of the silicone resin layer 14.
The porous membrane 12a is preferably made of a material having heat resistance and low hydrolyzability. Specific examples of such a porous membrane 12a include membrane filter membranes such as polysulfone (PSF), polyethersulfone, polypropylene (PP) and cellulose, interfacially polymerized thin films of polyamide and polyimide, polytetrafluoroethylene (PTFE). And a stretched porous membrane of high molecular weight polyethylene.
Especially, the porous membrane 12a containing 1 or more materials selected from fluorine-containing polymers, such as PTFE, PP, and PSF, is illustrated preferably. Among them, a stretched porous membrane of PTFE or high molecular weight polyethylene has a high porosity, has little inhibition of diffusion of acidic gas (especially carbon dioxide gas), and is preferable from the viewpoints of strength and suitability for production. In particular, a stretched porous membrane of PTFE is preferably used in terms of heat resistance and low hydrolyzability.

The auxiliary support membrane 12b is provided for reinforcing the porous membrane 12a.
Various materials can be used as the auxiliary support film 12b as long as it satisfies the required strength, stretch resistance and gas permeability. For example, a nonwoven fabric, a woven fabric, a net, and a mesh can be appropriately selected and used.

The auxiliary support membrane 12b is also preferably made of a material having heat resistance and low hydrolyzability, similar to the porous membrane 12a described above.
Considering this point, the fibers constituting the nonwoven fabric, woven fabric, and knitted fabric are excellent in durability and heat resistance, polyolefin such as polypropylene (PP), modified polyamide such as aramid (trade name), polytetrafluoro Fibers made of fluorine-containing resins such as ethylene and polyvinylidene fluoride are preferred. It is preferable to use the same material as the resin material constituting the mesh. Among these materials, a non-woven fabric made of PP that is inexpensive and has high mechanical strength is particularly preferably exemplified.

  When the support 12 has the auxiliary support film 12b, the mechanical strength can be improved. Therefore, even in the manufacturing method using RtoR in the illustrated example, wrinkles on the support 12 can be prevented, and productivity can be increased.

If the support 12 is too thin, the strength is difficult. Considering this point, the thickness of the porous membrane 12a is preferably 5 to 100 μm, and the thickness of the auxiliary support membrane 12b is preferably 50 to 300 μm.
When the support 12 is a single layer, the thickness of the support 12 is preferably 30 to 500 μm.

  The silicone resin layer 14 is a layer made of a compound having a so-called silicone bond or a silicone-containing compound. Specifically, linear silicones such as polydimethylsiloxane (PDMS), polymethylphenylsiloxane, polymethylhydrogensiloxane, etc., modified silicones introduced with amino groups, epoxy groups, halogenated alkyl groups, etc. in the side chains, Moreover, the layer which consists of a silicone resin which has gas permeability, such as silicon-containing polyacetylenes, such as polytrimethylsilyl propyne, is illustrated. Among these, PDMS and modified silicone of PDMS are preferably exemplified.

Here, in the present invention, the ratio of the protrusions on the surface of the silicone resin layer 14 used for forming the acidic gas separation layer 16 is 0.1 / μm ² to 50 / μm ² . In order to make the ratio of the protrusions on the surface of the silicone resin layer 14 in such a range, a filler is dispersed inside the silicone resin layer 14.
In addition, the measuring method of the ratio of the processus | protrusion of the surface of the silicone resin layer 14 in this invention is as follows.
Using a scanning electron microscope (SEM), obtain an SEM image of the surface of the silicone resin layer 14 in the range of 9 μm × 12 μm, and count the protrusions using the protrusions with a diameter of 100 nm or more as protrusions. The ratio of surface protrusions was determined.

From the viewpoint of adhesion and the like, the ratio of the protrusions on the surface of the silicone resin layer 14 is preferably 1 / μm ² to 30 / μm ² .

  As the filler material dispersed in the silicone resin layer 14, silica, aerosil, titania, alumina, carbon, boron nitride, talc, zeolite, or the like is preferably used. In particular, silica, titania, and zeolite are suitable.

Moreover, the average particle diameter of a filler can use suitably the thing of the range of 0.001 micrometer-30 micrometers. By setting the average particle diameter of the filler within this range, it is preferable in that the ratio of protrusions on the surface of the silicone resin layer 14 can be easily adjusted to a range of 0.1 / μm ² to 50 / μm ² .
The filler particle concentration in the silicone resin layer 14 is preferably in the range of 0.01 wt% to 50 wt%.
Further, as the shape of the filler, fillers having various shapes such as a spherical shape and a plate shape can be used.

A method for forming such a silicone resin layer 14 is not particularly limited, but the silicone resin layer 14 can be formed by applying a silicone coating solution to be the silicone resin layer 14 on the porous support 12.
The silicone coating solution for forming the silicone resin layer 14 is a monomer, dimer, trimer, oligomer, prepolymer, mixture of these compounds, a curing agent, a curing accelerator, a crosslinking agent, or a thickener. In addition to the reinforcing agent and the like, it contains the above filler.

In addition, it is preferable that a silicone coating liquid does not contain the organic solvent normally used when forming such a resin layer.
Since the silicone coating liquid does not contain an organic solvent, the drying process of the silicone coating liquid is not required, and the monomer can be cured immediately after the silicone coating liquid is applied. This is preferable from the viewpoint of making it unnecessary to install equipment and explosion-proof equipment.

Next, the manufacturing apparatus which produces the laminated body 10 of this invention using such a composite body 18 is demonstrated.
2 sends out the composite 18 from a composite roll 18R formed by winding the long composite 18 and transports the composite 18 in the longitudinal direction while separating the acidic gas into the silicone resin layer 14. The coating composition to be the layer 16 is applied. Next, the manufacturing apparatus 50 dries the coating composition to form the acidic gas separation layer 16 to obtain the acidic gas separation laminate 10 manufactured by the manufacturing method of the present invention. Furthermore, the manufacturing apparatus 20 winds the produced laminated body 10 for acid gas separation into a roll shape, and makes it the laminated body roll 10R.

Such a manufacturing apparatus 50 basically includes a supply unit 52, a coating unit 54, a drying device 56, and a winding unit 58.
In addition to the illustrated members, the manufacturing apparatus 50 manufactures a functional film (functional film) using RtoR, such as a pass roller (guide roller), a pair of transport rollers, a transport guide, and various sensors, as necessary. You may have various members provided in the apparatus to do.

The supply unit 52 is loaded with the composite roll 18R formed by winding the long composite 18 in a roll shape on the rotary shaft 61, and rotates the rotary shaft 61, that is, the composite roll 18R. This is the part to be sent out.
In addition, in the supply part 52, such a delivery and conveyance of the composite 18 may be performed by a known method.

The composite 18 delivered from the composite roll 18 </ b> R is transported in the longitudinal direction, and then transported to the coating unit 54, where a coating composition that becomes the acidic gas separation layer 16 is applied.
In the illustrated example, the coating unit 54 includes a coating device 62 and a backup roller 64. The composite 18 is conveyed in the longitudinal direction while being supported at a predetermined position by the backup roller 64, and the coating composition is applied to the surface of the silicone resin layer 14.
Here, as described above, the ratio of the protrusions on the surface of the silicone resin layer 14 used in the step of applying the coating composition to be the acidic gas separation layer 16 is 0.1 / μm ² to 50 / μm ² . is there.

  As described above, in the acidic gas separation laminate having the acidic gas separation layer, there is a problem in durability since the soft gel-like acidic gas separation layer enters the porous support by use. On the other hand, as shown in Patent Document 3 and the like, a porous support is formed by forming a silicone resin layer on the surface of the porous support and forming an acidic gas separation layer on the surface of the silicone resin layer. It is possible to prevent the acidic gas separation layer from entering.

However, as described above, when the coating solution of the acidic gas separation layer is applied onto the hydrophobic smooth silicone resin layer, the coating solution is repelled and the film thickness becomes non-uniform, or pores are formed. Therefore, there has been a problem that the acidic gas separation layer cannot be formed properly.
In addition, the acid gas separation layer needs to retain a large amount of moisture in the membrane in order for the carrier to function sufficiently. Therefore, a polymer having very high water absorption and water retention is used for the acidic gas separation layer. In addition, in the acidic gas separation layer, as the content of a carrier such as a metal carbonate increases, the amount of water absorption increases and the acidic gas separation performance is improved. That is, the acidic gas separation layer is often a very soft (low viscosity), gel membrane. On the other hand, the silicone resin layer is hydrophobic. Therefore, there is a problem that the adhesion between the formed acidic gas separation layer and the silicone resin layer is low.
Due to the above problems, there is a problem that the acidic gas separation layer is easily peeled off and the durability is low.

On the other hand, in the present invention, the acid gas separation layer 16 is formed on the silicone resin layer 14 by setting the ratio of the protrusions on the surface of the silicone resin layer 14 to 0.1 pieces / μm ² to 50 pieces / μm ^2. Since the coating liquid can be prevented from being repelled when the coating liquid is applied, the thickness of the acidic gas separation layer 16 formed on the silicone resin layer 14 can be made uniform, The acid gas separation layer 16 can be formed. Moreover, the roughness of the interface of the formed acidic gas separation layer 16 and the silicone resin layer 14 can be roughened, and adhesiveness can be improved by an anchor effect. Therefore, it is possible to prevent the acidic gas separation layer from peeling off and increase durability.

In addition, the point which can suppress the repelling of the coating liquid at the time of apply | coating a coating liquid on the silicone resin layer 14 more suitably, and the adhesiveness of the acidic gas separation layer 16 and the silicone resin layer 14 of the produced laminated body 10 are improved. The ratio of the protrusions on the surface of the silicone resin layer 14 is more preferably 1 piece / μm ² to 50 pieces / μm ² in that it can be further improved.

In the production method of the present invention, the conveyance speed of the composite 18 when forming the acidic gas separation layer 16 may be set as appropriate according to the type of the composite 18 and the viscosity of the coating composition.
Here, when the conveyance speed of the composite 18 is too fast, there is a possibility that the coating film thickness uniformity of the coating composition is reduced and the coating composition is insufficiently dried, and when it is too slow, the productivity is lowered. . Considering this point, the conveyance speed of the composite 18 is preferably 0.5 m / min or more, more preferably 0.75 to 200 m / min, and particularly preferably 1 to 200 m / min.

The acidic gas separation layer 16 contains a hydrophilic compound such as a hydrophilic polymer, a carrier that reacts with the acidic gas, water, and the like.
Therefore, the coating composition for forming such an acidic gas separation layer 16 is a composition containing a hydrophilic compound, a carrier and water (room temperature water or warm water), or a necessary component such as a crosslinking agent. (Paint / coating liquid). The hydrophilic compound may be crosslinked, partially crosslinked, or uncrosslinked, or a mixture of these.

  The hydrophilic compound functions as a binder, and retains moisture in the acidic gas separation layer 16 to exhibit a function of separating a gas such as carbon dioxide by a carrier. Moreover, it is preferable that a hydrophilic compound has a crosslinked structure from a heat resistant viewpoint.

From the viewpoint that the hydrophilic compound can be dissolved in water to form a coating solution, and the acidic gas separation layer 16 preferably has high hydrophilicity (moisturizing property), those having high hydrophilicity are preferable.
Specifically, the hydrophilic compound preferably has a hydrophilicity of 0.5 g / g or more, more preferably 1 g / g or more, more preferably 5 g / g of the physiological saline. More preferably, it has a hydrophilicity of g or more, particularly preferably has a hydrophilicity of 10 g / g or more, and most preferably has a hydrophilicity of 20 g / g or more.

What is necessary is just to select the weight average molecular weight of a hydrophilic compound suitably in the range which can form a stable film | membrane. Specifically, 20,000 to 2,000,000 is preferable, 25,000 to 2,000,000 is more preferable, and 30,000 to 2,000,000 is particularly preferable.
By setting the weight average molecular weight of the hydrophilic compound to 20,000 or more, the acidic gas separation layer 16 having a sufficient membrane strength can be obtained stably.
In particular, when the hydrophilic compound has —OH as a crosslinkable group, the hydrophilic compound preferably has a weight average molecular weight of 30,000 or more. In this case, the weight average molecular weight is more preferably 40,000 or more, and more preferably 50,000 or more. When the hydrophilic compound has —OH as a crosslinkable group, the weight average molecular weight is preferably 6,000,000 or less from the viewpoint of production suitability.
Also, when having -NH ₂ as crosslinkable groups, hydrophilic compounds are those preferably has a weight average molecular weight of 10,000 or more. In this case, the weight average molecular weight of the hydrophilic compound is more preferably 15,000 or more, and particularly preferably 20,000 or more. When the hydrophilic compound has —NH ₂ as a crosslinkable group, the weight average molecular weight is preferably 1,000,000 or less from the viewpoint of production suitability.
For example, when PVA is used as the hydrophilic compound, the weight average molecular weight of the hydrophilic compound may be a value measured according to JIS K 6726. Moreover, when using a commercial item, what is necessary is just to use the molecular weight nominally mentioned in a catalog, a specification, etc.

As the crosslinkable group forming the hydrophilic compound, those capable of forming a hydrolysis-resistant crosslinked structure are preferably selected.
Specific examples include a hydroxy group, an amino group, a chlorine atom, a cyano group, a carboxy group, and an epoxy group. Among these, an amino group and a hydroxy group are preferably exemplified. Furthermore, most preferably, a hydroxy group is illustrated from the viewpoint of affinity with a carrier and a carrier carrying effect.

  Specific examples of hydrophilic compounds include those having a single crosslinkable group such as polyallylamine, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethyleneimine, polyvinylamine, polyornithine, polylysine, Examples include polyethylene oxide, water-soluble cellulose, starch, alginic acid, chitin, polysulfonic acid, polyhydroxymethacrylate, poly-N-vinylacetamide and the like. Most preferred is polyvinyl alcohol. Moreover, as a hydrophilic compound, these copolymers are also illustrated.

Examples of the hydrophilic compound having a plurality of crosslinkable groups include polyvinyl alcohol-polyacrylic acid copolymers. A polyvinyl alcohol-polyacrylic salt copolymer is preferable because of its high water absorption ability and high hydrogel strength even at high water absorption.
The content of polyacrylic acid in the polyvinyl alcohol-polyacrylic acid copolymer is, for example, 1 to 95 mol%, preferably 2 to 70 mol%, more preferably 3 to 60 mol%, and particularly preferably 5 to 50 mol%. It is. The content of acrylic acid can be controlled by a known synthesis method.
In the polyvinyl alcohol-polyacrylic acid copolymer, the polyacrylic acid may be a salt. Examples of the polyacrylic acid salt in this case include ammonium salts and organic ammonium salts in addition to alkali metal salts such as sodium salts and potassium salts.

Polyvinyl alcohol is also available as a commercial product. Specific examples include PVA117 (manufactured by Kuraray Co., Ltd.), poval (manufactured by Kuraray), polyvinyl alcohol (manufactured by Aldrich), J-poval (manufactured by Nippon Vinegarten Poval). Although there are various molecular weight grades, those having a weight average molecular weight of 130,000 to 300,000 are preferred.
A polyvinyl alcohol-polyacrylate copolymer (sodium salt) is also available as a commercial product. For example, Crustomer AP20 (made by Kuraray Co., Ltd.) is exemplified.

  In addition, in the manufacturing method of this invention, you may mix and use 2 or more types for the hydrophilic compound of the acidic gas separation layer 16 to form.

The content of the hydrophilic compound in the coating composition is such that the hydrophilic compound functions as a binder and can sufficiently retain moisture in the formed acidic gas separation layer 16, and the kind of the hydrophilic composition or carrier, etc. It may be set appropriately according to the above.
Specifically, the amount in the acidic gas separation layer 16 is preferably 0.5 to 50% by mass, more preferably 0.75 to 30% by mass, and 1 to 15% by mass. Is particularly preferred. By setting the content of the hydrophilic compound within this range, the above-mentioned function as a binder and the moisture retention function can be stably and suitably expressed.

The crosslinked structure of the hydrophilic compound can be formed by a known method such as thermal crosslinking, ultraviolet crosslinking, electron beam crosslinking, radiation crosslinking, or photocrosslinking.
Photocrosslinking or thermal crosslinking is preferred, and thermal crosslinking is most preferred.

Moreover, it is preferable that a coating composition contains a crosslinking agent.
As the crosslinking agent, one containing a crosslinking agent that reacts with a hydrophilic compound and has two or more functional groups capable of crosslinking such as thermal crosslinking or photocrosslinking is selected. The formed crosslinked structure is preferably a hydrolysis-resistant crosslinked structure.
From such a viewpoint, as a crosslinking agent added to the coating composition, an epoxy crosslinking agent, a polyvalent glycidyl ether, a polyhydric alcohol, a polyvalent isocyanate, a polyvalent aziridine, a haloepoxy compound, a polyvalent aldehyde, a polyvalent amine, An organic metal type crosslinking agent etc. are illustrated suitably. More preferred are polyvalent aldehydes, organometallic crosslinking agents and epoxy crosslinking agents, and among them, polyvalent aldehydes such as glutaraldehyde and formaldehyde having two or more aldehyde groups are preferred.

As an epoxy crosslinking agent, it is a compound which has 2 or more of epoxy groups, and the compound which has 4 or more is also preferable. Epoxy crosslinking agents are also available as commercial products, for example, trimethylolpropane triglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., Epolite 100MF, etc.), Nagase ChemteX Corporation EX-411, EX-313, EX-614B, Examples include EX-810, EX-811, EX-821, EX-830, NOF Corporation Epiol E400, and the like.
Moreover, the oxetane compound which has cyclic ether as a compound similar to an epoxy crosslinking agent is also used preferably. The oxetane compound is preferably a polyvalent glycidyl ether having two or more functional groups, and commercially available products include, for example, EX-411, EX-313, EX-614B, EX-810, EX-811, EX manufactured by Nagase ChemteX Corporation. -821, EX-830, and the like.

  Examples of the polyvalent glycidyl ether include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene Examples include glycol glycidyl ether and polypropylene glycol diglycidyl ether.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, triethanolamine, polyoxypropyl, and oxyethylene oxypropylene block copolymer. Examples include coalescence, pentaerythritol, and sobitol.

Examples of the polyvalent isocyanate include 2,4-toluylene diisocyanate and hexamethylene diisocyanate.
Examples of the polyvalent aziridines include 2,2-bishydroxymethylbutanol-tris [3- (1-acylidinyl) propionate], 1,6-hexamethylenediethyleneurea, diphenylmethane-bis-4,4′-N, N. Examples include '-diethylene urea.

Examples of the haloepoxy compound include epichlorohydrin and α-methylchlorohydrin.
Examples of the polyvalent aldehyde include glutaraldehyde and glyoxal.
Examples of the polyvalent amine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine.
Furthermore, examples of the organometallic crosslinking agent include organic titanium crosslinking agents and organic zirconia crosslinking agents.

For example, when polyvinyl alcohol having a weight average molecular weight of 130,000 or more is used as the hydrophilic compound, it is possible to form a crosslinked structure having good reactivity with this hydrophilic compound and excellent hydrolysis resistance. Therefore, an epoxy crosslinking agent and glutaraldehyde are preferably used.
Moreover, when using a polyvinyl alcohol-polyacrylic acid copolymer as a hydrophilic compound, an epoxy crosslinking agent and glutaraldehyde are preferably utilized.
In addition, when a polyallylamine having a weight average molecular weight of 10,000 or more is used as the hydrophilic compound, it is possible to form a crosslinked structure that has good reactivity with the hydrophilic compound and excellent hydrolysis resistance. Therefore, an epoxy crosslinking agent, glutaraldehyde, and an organometallic crosslinking agent are preferably used.
Further, when polyethyleneimine or polyallylamine is used as the hydrophilic compound, an epoxy crosslinking agent is preferably used.

What is necessary is just to set the quantity of a crosslinking agent suitably according to the kind of hydrophilic compound and crosslinking agent which are added to a coating composition.
Specifically, the amount is preferably 0.001 to 80 parts by weight, more preferably 0.01 to 60 parts by weight, and particularly preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the crosslinkable group possessed by the hydrophilic compound. preferable. By setting the content of the cross-linking agent in the above range, a facilitated transport film having good cross-linking structure formation and excellent shape maintainability can be obtained.
Further, when focusing on the crosslinkable group possessed by the hydrophilic compound, the crosslinked structure is formed by reacting 0.001 to 80 mol of a crosslinking agent with respect to 100 mol of the crosslinkable group possessed by the hydrophilic compound. preferable.

In the acid gas separation layer 16, the carrier (acid gas carrier) reacts with an acid gas (for example, carbon dioxide gas (CO ₂ )) to transport the acid gas.

The carrier is a water-soluble compound having affinity with acidic gas and showing basicity. Specific examples include alkali metal compounds, nitrogen-containing compounds, and sulfur oxides.
The carrier may react indirectly with the acid gas, or the carrier itself may react directly with the acid gas.
The former reacts with other gas contained in the supply gas, shows basicity, and the basic compound reacts with acidic gas. More specifically, OH react with steam (water) ^- was released, the OH ^- that reacts with CO _2, compounds which can be incorporated selectively CO ₂ in the acid gas separation layer 16 For example, an alkali metal compound.
The latter is such that the carrier itself is basic, for example, a nitrogen-containing compound or a sulfur oxide.

  Examples of the alkali metal compound include alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxides. Here, as the alkali metal, an alkali metal element selected from cesium, rubidium, potassium, lithium, and sodium is preferably used. In addition, in this invention, an alkali metal compound contains the salt and its ion other than alkali metal itself.

Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.
Examples of the alkali metal bicarbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.
Furthermore, examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.
Among these, alkali metal carbonates are preferable, and compounds having high solubility in water, potassium, rubidium, and cesium are preferable from the viewpoint of good affinity with acidic gas.

Moreover, when using an alkali metal compound as a carrier, two or more kinds of carriers may be used in combination.
When two or more kinds of carriers are present in the acidic gas separation layer 16, different carriers can be separated from each other in the film. As a result, due to the difference in deliquescence of the plurality of carriers, the acid gas separation layers 16 or the acid gas separation layers 16 and other members are attached to each other due to the water absorption of the acid gas separation layers 16 during production. Wearing (blocking) can be suitably suppressed.
Moreover, when using 2 or more types of alkali metal compounds as a carrier by the point of being able to obtain the blocking inhibitory effect more suitably, the deliquescence property is more excellent than the first compound having deliquescence and the first compound. It is preferable to include a second compound having a low specific gravity. As an example, the first compound is exemplified by cesium carbonate, and the second compound is exemplified by potassium carbonate.

Nitrogen-containing compounds include amino acids such as glycine, alanine, serine, proline, histidine, taurine, diaminopropionic acid, hetero compounds such as pyridine, histidine, piperazine, imidazole, triazine, monoethanolamine, diethanolamine, triethanolamine , Alkanolamines such as monopropanolamine, dipropanolamine and tripropanolamine, cyclic polyetheramines such as cryptand [2.1] and cryptand [2.2], cryptand [2.2.1] and cryptand [ And bicyclic polyetheramines such as 2.2.2], porphyrin, phthalocyanine, ethylenediaminetetraacetic acid and the like.
Further, examples of the sulfur compound include amino acids such as cystine and cysteine, polythiophene, dodecylthiol and the like.

What is necessary is just to set content of the carrier in a coating composition suitably according to the kind etc. of a carrier or a hydrophilic compound. Specifically, the amount of the carrier in the acidic gas separation layer 16 is preferably 0.3 to 30% by mass, more preferably 0.5 to 25% by mass, and 1 to 20% by mass. The amount is particularly preferred.
By setting the content of the carrier in the coating composition within the above range, salting out before coating can be suitably prevented, and the formed acidic gas separation layer 16 reliably exhibits the separation function of acidic gas. it can.
Moreover, the amount ratio of the hydrophilic compound to the carrier in the coating composition is preferably 1: 9 to 2: 3 or less, more preferably 1: 4 to 2: 3 or less, in terms of the hydrophilic compound: carrier mass ratio. : 7-2: 3 is particularly preferable.

The coating composition may contain a thickener as necessary.
As the thickener, for example, thickening polysaccharides such as agar, carboxymethylcellulose, carrageenan, chitansan gum, guar gum and pectin are preferable. Among these, carboxymethylcellulose is preferable from the viewpoints of film forming property, availability, and cost.
By using carboxymethyl cellulose, a coating composition having a desired viscosity can be easily obtained with a small amount of content, and at least a part of components other than the solvent contained in the coating solution cannot be dissolved in the coating solution and deposited. There is little fear of it.

The content of the thickener in the coating composition is preferably as small as possible as long as the content of the thickener in the composition (coating liquid) can be adjusted to the target viscosity.
As a general index, 10% by mass or less is preferable, 0.1 to 5% by mass is more preferable, and 0.1 to 2% by mass or less is more preferable.

  The coating composition (acid gas separation layer 16) may contain various components as necessary in addition to such a hydrophilic compound, a crosslinking agent and a carrier, or a thickener.

Examples of such components include an antioxidant such as dibutylhydroxytoluene (BHT), a compound having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms and a hydrophilic group, and a siloxane structure. Specific compounds such as compounds having a surfactant, surfactants such as sodium octoate and sodium 1-hexasulfonate, polymer particles such as polyolefin particles and polymethyl methacrylate particles, and the like.
In addition, a catalyst, a moisturizing (moisture absorbing) agent, an auxiliary solvent, a film strength adjusting agent, a defect detecting agent and the like may be used as necessary.

What is necessary is just to prepare a coating composition by a well-known method. That is, first, a hydrophilic compound, a carrier, and various components to be added as needed are respectively added to water (room temperature water or warm water) in appropriate amounts, and sufficiently stirred, so that an acidic gas separation layer is obtained. A coating composition to be 16 is prepared.
In the preparation of the coating composition, if necessary, dissolution of each component may be promoted by heating with stirring. Moreover, after adding a hydrophilic compound to water and melt | dissolving, precipitation (salting out) of a hydrophilic compound can be effectively prevented by adding a carrier gradually and stirring.

Here, it is preferable that the coating composition used as the acidic gas separation layer 16 has a viscosity at 25 ° C. of 100 cp or more.
By setting the viscosity at 25 ° C. of the coating composition to 100 cp or more, repellency when the coating composition is applied on the silicone resin layer 14 can be suppressed, the uniformity of coating of the coating composition can be improved, etc. This is preferable.
In the production method of the present invention, the viscosity of the coating composition at the time of coating may be measured by a method according to JIS Z8803, and the viscosity at a rotational speed of 60 rpm using a B-type viscometer or a viscometer similar thereto. May be measured as the temperature of the coating composition at the time of coating.

The surface tension of the coating composition is preferably 63 mN / m or less.
By making the surface tension of a coating composition into the said range, it is preferable at the point which can apply | coat a coating composition on the board | substrate which has water repellency like a silicone resin layer suitably.
In the present invention, the surface tension of the coating composition is measured with a fully automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.

As described above, the application part 54 is a part for applying such an application composition to the composite 18 (silicone resin layer 14) conveyed in the longitudinal direction.
In the illustrated example, the application unit 54 includes an application device 62 and a backup roller 64. That is, the composite 18 is transported while being kept at a predetermined application position by the backup roller 64 and is applied with the coating composition by the coating device 62 to form a coating film (liquid film) of the coating composition. In addition, in the application part 54, you may perform temperature control of a coating composition, the composite_body | complex 18, etc. as needed.

Various known devices can be used as the coating device 62.
Specifically, roll coater, direct gravure coater, offset gravure coater, 1 roll kiss coater, 3 reverse roll coater, forward rotation roll coater, curtain flow coater, extrusion die coater, air doctor coater, blade coater, rod coater And knife coaters, squeeze coaters, reverse roll coaters, bar coaters and the like.
In consideration of the preferable viscosity of the coating composition, the coating amount of the coating composition, and the like, a roll coater, a bar coater, a positive rotation roll coater, a knife coater, and the like are preferably used.

Here, in the production method of the present invention, when the acidic gas separation layer 16 is formed, the coating device 62 has a coating thickness (the thickness of the coating composition applied to the composite 18) of 0. It is preferable to apply the coating composition to the support 12 so that the thickness is 05 to 2 mm.
By setting the thickness of the coating film of the coating composition within the above range, it is possible to form the acidic gas separation layer 16 that appropriately expresses the target function, and to prevent the occurrence of defects due to the mixing of bubbles and foreign matters. This is preferable in that sufficient drying can be performed by the drying device 56 described later.
Moreover, when the above point is considered, as for the thickness of the coating film used as the acidic gas separation layer 16, 0.1-1.5 mm is more preferable.

Moreover, in the manufacturing method of this invention, the film thickness of the acidic gas separation layer 16 formed by drying of the coating composition mentioned later is a film thickness which can obtain the target performance according to the composition of the acidic gas separation layer 16, etc. May be set as appropriate. Specifically, 3-1000 μm is preferable, and 5-500 μm is more preferable. In addition, it is preferable that the coating composition is prepared so that the acidic gas separation layer 16 has the above-described coating film thickness and the acidic gas separation layer 16 having this thickness can be obtained.
By setting the film thickness of the acidic gas separation layer 16 within the above range, it is preferable in terms of improving gas permeation performance and suppressing the occurrence of defects.

  In the production method of the present invention, a plurality of facilitated transport films having the same composition or different compositions may be formed.

The composite 18 coated with the coating composition in the coating unit 54 is guided to the pass roller 68 a that contacts the back surface (the surface opposite to the coating surface of the coating composition) and is conveyed to the drying device 56.
The drying device 56 (drying step) removes at least a part of water from the coating composition coated on the support 12 and dries (or further crosslinks the hydrophilic compound), thereby forming the acidic gas separation layer 16. It is a site | part which forms and produces the laminated body 10 for acidic gas separation.

As the drying method, various known methods for drying by removing water, such as hot air drying or a drying method by heating the support 12, can be used.
When performing warm air drying, the speed of the warm air may be set as appropriate so that the coating composition can be dried quickly and the coating film (gel film) of the coating composition does not collapse. Specifically, 0.5 to 200 m / min is preferable, 0.75 to 200 m / min is more preferable, and 1 to 200 m / min is particularly preferable.
Further, the temperature of the hot air may be appropriately set at a temperature at which the support 12 is not deformed and the coating composition can be dried quickly. Specifically, the film surface temperature is preferably 1 to 120 ° C, more preferably 2 to 115 ° C, and particularly preferably 3 to 110 ° C.

When drying the support 12 by heating, the temperature at which the support 12 is not deformed and the coating composition can be dried quickly may be set as appropriate. Moreover, you may use blowing of a dry wind for heating of the support body 12 together.
Specifically, the temperature of the support 12 is preferably 60 to 120 ° C, more preferably 60 to 90 ° C, and particularly preferably 70 to 80 ° C. In this case, the film surface temperature is preferably 15 to 80 ° C, and more preferably 30 to 70 ° C.

The composite 18, that is, the acidic gas separation laminate 10, from which the coating film of the coating composition has been dried by the drying device 56, is guided by the pass roller 68 b and conveyed to the winding unit 58.
The winding unit 58 winds the acidic gas separating laminate 10 around the winding shaft 70 to form a laminate roll 10R.

The winding unit 58 includes the above-described winding shaft 70 and three pass rollers 68c to 68e.
The acidic gas separating laminate 10 is guided along a predetermined transport path by the pass rollers 68c to 68e and wound around the take-up shaft 70 (laminate roll 10R) to form a laminate roll 10R. The three pass rollers 68c to 68e also act as tension cutters, and guide the acid gas separation laminate 10 and the like to meander.

  Hereinafter, by explaining an example of the operation of the production apparatus 50, the production method of the composite of the present invention will be described in more detail.

First, the composite roll 18R is mounted on the rotating shaft 61 of the supply unit 52 of the manufacturing apparatus 50, and the rotating shaft 61 is rotated to feed the composite 18 from the composite roll 18R. Subsequently, the composite 18 sent out from the composite roll 18R passes through the coating unit 54 (backup roller 64), the pass roller 68a, the drying device 56, the pass roller 68b, and the pass rollers 68c to 68e, and reaches a take-up shaft 70. The tip of the composite 18 is wound around the winding shaft 70.
Here, as shown in FIG. 1, the composite 18 has a two-layer structure including a porous membrane 12a and an auxiliary support membrane 12b, and a silicone resin layer 14 is provided on the surface of the porous membrane 12a. It is. Further, a filler is dispersed inside the silicone resin layer 14, and the ratio of protrusions on the surface is in the range of 0.1 / μm ² to 50 / μm ² .
The composite roll 18R is attached to the rotating shaft 61 so that the silicone resin layer 14 side faces the coating device 62.

  Further, the coating device 62 is filled with a necessary amount of the coating composition. As described above, the coating composition preferably has a viscosity at 25 ° C. of 100 cp or more.

  When the composite 18 is passed through a predetermined conveyance path and the coating device 62 is filled with the coating composition, the rotary shaft 61, the winding shaft 70, the backup roller 64, and the like are driven in synchronism with each other. Start conveyance.

  The composite 18 sent out from the composite roll 18R is first transported in the longitudinal direction while being supported at a predetermined application position by the backup roller 64 in the coating unit 54 while being transported in the longitudinal direction. The coating composition to be the acidic gas separation layer 16 is applied so as to have a predetermined coating thickness (coating amount).

The composite 18 coated with the coating composition to be the acidic gas separation layer 16 is then guided by the pass roller 68a to reach the drying device 56, and the coating composition is dried in the drying device 56, thereby separating the acidic gas. The laminated body 10 for acid gas separation produced by the production method of the present invention in which the layer 16 is formed.
The acidic gas separation laminate 10 is guided by the pass roller 68b and conveyed to the take-up unit 58, guided along a predetermined conveyance path by the pass rollers 68c to 68e, and taken up by the take-up shaft 70, and the laminate roll. 10R.

Here, in the above embodiment, by dispersing a filler in the inside of the silicone resin layer 14, the ratio of the protrusions of the surface of the silicone resin layer 14 is 0.1 pieces / [mu] m ² to 50 pieces / [mu] m ² However, the present invention is not limited to this, and a surface roughening treatment such as plasma treatment or chemical etching may be performed so that the ratio of protrusions on the surface of the silicone resin layer falls within the above range.

FIG. 3 is a diagram conceptually illustrating an example of a manufacturing apparatus that performs one process of another example of the manufacturing method of the present invention.
The manufacturing apparatus 20 shown in FIG. 3 uses a long porous support 12, and after applying and curing a silicone coating solution to be a silicone resin layer 14 on the surface of the porous support 12 by RtoR, a silicone resin The surface of the layer 14 is roughened to produce a composite 18 (composite roll 18R).

As described above, in the manufacturing apparatus 20 shown in FIG. 3, the composite 18 is manufactured using RtoR. Therefore, the production apparatus 20 sends out the porous support 12 from a support roll 12R formed by winding the long porous support 12 (web-like porous support 12) into a roll, and the porous support While transporting 12 in the longitudinal direction, a silicone coating solution that becomes the silicone resin layer 14 is applied to the surface of the porous support 12. Next, the manufacturing apparatus 20 cures the silicone coating solution applied to the porous support 12 to form the silicone resin layer 14. The manufacturing apparatus 20 further performs a roughening process on the surface of the silicone resin layer 14 so that the ratio of the protrusions on the surface of the silicone resin layer 14 is 0.1 / μm ² to 50 / μm ^2. The composite 18 is obtained by forming the silicone resin layer 14 on the surface of the support 12. Furthermore, the manufacturing apparatus 20 winds (winds up) the composite body 18 produced in this way into a roll shape to obtain a composite roll 18R.

Such a manufacturing apparatus 20 basically includes a supply unit 24, a coating unit 26, a curing device 28, a winding unit 30, and a roughening treatment device 36.
Similar to the previous manufacturing apparatus 50, in the manufacturing apparatus 20, in addition to the illustrated members, various devices such as a pass roller and various sensors, which are provided in an apparatus for manufacturing a functional film by RtoR, may be provided. You may have a member.

The supply unit 24 loads a support roll 12R formed by winding the long porous support 12 in a roll shape around the rotation shaft 31, and the rotation shaft 31 (that is, the support roll 12R) is loaded on the rotation shaft 31. It is a part which sends out the porous support body 12 by rotating.
In addition, like the previous manufacturing apparatus 50, in the supply part 24, such a delivery and conveyance of the porous support body 12 should just be performed by a well-known method.

The support 12 sent out from the support roll 12R is then transported to the coating unit 26, and is coated with a silicone coating liquid that becomes the silicone resin layer 14 while being transported in the longitudinal direction.
In the illustrated example, the application unit 26 includes an application device 32 and a backup roller 34. The support 12 is conveyed in the longitudinal direction while being supported at a predetermined position by the backup roller 34, and the silicone coating liquid is applied to the surface of the porous film 12a.
In addition, the one where the conveyance speed of the support body 12 is quick from a viewpoint of productivity is preferable. However, in order to apply | coat a silicone coating liquid uniformly, 1-200 m / min is preferable, 3-150 m / min is more preferable, 5-120 m / min is especially preferable.

The support 12 is transported in the longitudinal direction while being positioned at a predetermined application position by the backup roller 34, and a silicone coating liquid is applied to the surface of the porous film 12 a by the coating device 32, and a coating film of the coating liquid (liquid Film).
In addition, in the application part 26, you may perform temperature control of a silicone coating liquid, the support body 12, etc. as needed.

As the coating device 32, various known devices can be used, and the same devices as the above-described coating device 62 are exemplified.
Among these, considering the control of the viscosity of the silicone coating solution, the coating amount of the silicone coating solution, the penetration amount of the silicone resin, etc., a roll coater, a direct gravure coater, an offset gravure coater, a single roll kiss coater, a three reverse roll coater, A forward rotating roll coater, a squeeze coater, a reverse roll coater, or the like is preferably used.

Here, it is preferable that the coating device 32 applies the silicone coating liquid to the surface of the porous film 12a so that the thickness of the cured silicone resin layer 14 is 10 μm or less. That is, in the manufacturing method of the present invention, the thickness of the silicone resin layer 14 to be formed is preferably 10 μm or less.
In the present invention, the film thickness of the silicone resin layer 14 refers to the silicone resin layer 14 formed on the surface of the porous film 12a (on the porous film 12a) that does not include the portion soaked into the porous film 12a. Is the film thickness.

By setting the film thickness of the silicone resin layer 14 to 10 μm or less, it is preferable in terms of suitably preventing a decrease in gas permeability due to the silicone resin layer 14.
Considering the above points, the thickness of the silicone resin layer 14 is more preferably 5 μm or less.

Further, the silicone resin layer 14 may be thin as long as it covers the entire surface of the porous film 12a with a dense film without coming off.
Considering this point, the thickness of the silicone resin layer 14 is preferably 0.01 μm or more. By setting the thickness of the silicone resin layer 14 to 0.01 μm or more, the surface of the porous membrane 12a is suitably covered with the dense silicone resin layer 14, and the facilitated transport membrane enters the porous membrane 12a. The composite 18 that can be more suitably prevented is obtained.

  The film thickness of the silicone resin layer 14 may be controlled by conducting experiments and simulations in advance in consideration of the penetration of the silicone coating solution into the porous film 12a.

The support 12 coated with the silicone coating liquid in the coating unit 26 is then conveyed to the curing device 28 (drying process). The curing device 28 is preferably arranged immediately after (directly downstream) the application unit 26 in the support conveyance direction.
While the support 12 is conveyed in the longitudinal direction by the curing device 28, the silicone coating liquid is cured (crosslinking of the monomer and the like), and the silicone resin layer 14 is formed on the surface of the support 12 (porous film 12 a). The composite 18 is obtained.

For curing the silicone coating solution in the curing device 28, a method capable of curing the silicone coating solution may be appropriately used according to the type of monomer or the like contained in the silicone coating solution.
Specifically, ultraviolet irradiation, electron beam irradiation, heating, humidification and the like are exemplified.
Among them, the curing of the silicone coating solution by ultraviolet irradiation or short heating is preferably used for the reason that curling (deformation) of the support 12 can be suppressed and deterioration of the resin constituting the support 12 can be prevented. In particular, curing by ultraviolet irradiation is most preferably used. That is, in the production method of the present invention, it is preferable to form the silicone resin layer 14 with a silicone coating solution using a monomer or the like that can be cured by irradiation with ultraviolet rays.

  The silicone coating solution may be cured in an inert atmosphere such as a nitrogen atmosphere as necessary.

Here, in the production method of the present invention, it is preferable to form the silicone resin layer 14 by curing the silicone coating solution within 5 seconds after coating the silicone coating solution.
In the production method of the present invention, by using RtoR, the silicone coating solution can be cured in a short time after the silicone coating solution is applied.

The support 12 on which the silicone resin layer is formed in the curing device is then conveyed to the roughening treatment device 36.
The surface of the silicone resin layer is roughened while the support 12 is conveyed in the longitudinal direction by the roughening treatment device 36, and the ratio of protrusions on the surface to the surface of the support 12 (porous film 12 a). Is a composite 18 in which the silicone resin layer 14 of 0.1 / μm ² to 50 / μm ² is formed.

As a surface roughening method performed by the surface roughening apparatus 36, a surface roughening method such as plasma processing or chemical etching can be used.
As a surface roughening method performed by plasma treatment, for example, an inert gas such as nitrogen, argon (Ar), helium (He), or xenon (Xe) is used, and the gas pressure is set to 0.01 Pa to Conventional plasma processing, such as a method in which a vacuum is set to about 100 Pa, an object to be processed is placed between electrode pairs for forming plasma, and processing is performed by applying power for generating plasma to the electrode pairs. A surface roughening method can be used.
Further, as a surface roughening method performed by chemical etching, a treatment liquid (for example, hydrogen fluoride) having corrosiveness to the silicone resin layer is applied to the surface to dissolve the surface of the silicone resin layer. A conventional surface roughening method using chemical etching, such as a method, can be used.

The composite 18 having the silicone resin layer 14 roughened by the roughening treatment device 36 is guided by the pass rollers 38 a, 38 b, 38 c and 38 d and is conveyed to the winding unit 30.
The pass rollers 38b, 38c, and 38d also function as tension cutters, and guide the composite 18 to meander.

The winding unit 30 winds the composite 18 to form a composite roll 18R, and includes a pass roller 38e and a winding shaft 40.
The composite 18 conveyed to the take-up unit 30 is guided to the take-up shaft 40 by the pass roller 38e, and taken up by the take-up shaft 40 to be a composite roll 18R.

In the production method of the present invention, after the silicone coating liquid is applied and cured on the surface of the support 12 in this way to form the silicone resin layer 14, the surface of the silicone resin layer 14 is subjected to a roughening treatment. Then, after forming the composite 18 having a protrusion ratio on the surface of the silicone resin layer 14 of 0.1 / μm ² to 50 / μm ² , the silicone resin of the composite 18 is obtained by the manufacturing apparatus 50 shown in FIG. The acidic gas separation layer 16 may be formed on the surface of the layer 14.

In addition, the structure which disperse | distributes a filler in the inside of the silicone resin layer 14, and adjusts the ratio of the processus | protrusion on the surface is compared with the structure which roughens the silicone resin layer 14 by plasma treatment etc., and the bending tolerance of a film | membrane It is suitable in terms of gas permeability and film hardening properties of the silicone resin layer.
On the other hand, the configuration in which the silicone resin layer 14 is roughened by plasma treatment or the like can improve film hydrophilicity on the surface of the silicone resin layer 14, which can reduce film defects, compared with the configuration in which the silicone resin layer 14 is roughened using a filler. This is preferable in that it can be performed.
Moreover, it is good also as a structure which disperse | distributes a filler in the inside of the silicone resin layer 14, and also roughens the silicone resin layer 14 by processing, such as a plasma processing. By combining the dispersion of the filler and the plasma treatment to roughen the surface, the acidic gas separation layer 16 is less likely to be peeled off due to the effect of roughening by the protrusions and the improvement in hydrophilicity. Defects can be reduced.

3 includes only the coating device 32, the curing device 28, and the roughening treatment device 36, and the manufacturing device 50 illustrated in FIG. 2 includes only the coating device 62 and the drying device 56. That is, when this apparatus is used, the silicone resin layer 14 and the acid gas separation layer 16 are formed by separate apparatuses.
However, in the manufacturing method of the present invention, as conceptually shown in FIG. 4, using a device having a coating device 32, a curing device 28, a roughening treatment device 36, a coating device 62 and a drying device 56, It is also possible to form the acidic gas separation laminate 10 by forming the silicone resin layer 14 and the acidic gas separation layer 16 by performing feeding and winding from the roll by RtoR once.

  The acidic gas separation laminate 10 formed by the production method of the present invention can be used for various separation membrane modules. For example, it is laminated with a supply gas flow path member that becomes a raw material gas flow path and a permeate gas flow path member that becomes a separated acidic gas flow path, and spirally formed around a perforated central tube It is wound and used for a spiral type separation membrane module.

FIG. 5 is a diagram conceptually showing an example of an acid gas separation module using the acid gas separation laminate produced by the production method of the present invention.
An acid gas separation module (hereinafter also referred to as a separation module) 100 shown in FIG. 5 includes a center tube 112, an acid gas separation laminate 10, a supply gas flow path member 124, and a permeate gas flow path member 126. The module laminate 114 and the telescope prevention plate 116 are configured.

The separation module 100 is configured by laminating a plurality of sheet-like module laminates 114 and winding them around a central cylinder 112 having a plurality of through holes 112a on the peripheral surface, and both ends of the wound product of the module laminate 114. The telescope prevention plate 116 is provided on the surface through the central tube 112. In addition, the outermost peripheral surface of the wound module laminate 114 is covered with a gas impermeable coating layer 118.
Reference numeral 130 denotes an adhesive layer that bonds the acid gas separation laminate 10 (porous support 12) and the permeate gas flow path member 126 together.

In such a separation module 100, the raw material gas G from which the acidic gas is separated is supplied to the end face of the module laminate 114, for example, through the telescope prevention plate 116 (the opening 116d) on the far side in FIG. Then, the acid gas Gc is separated while flowing in the module laminate 114.
The acidic gas Gc separated from the raw material gas G by the module laminate 114 passes through the inside of the central cylinder 112 from the through hole 112a and is discharged from the open end 112b of the central cylinder 112. On the other hand, the source gas G from which the acid gas has been separated (hereinafter referred to as the residual gas Gr for convenience) is discharged from the end surface opposite to the supply side of the module laminate 114, and the telescope prevention plate 116 It is discharged to the outside of the separation module 100 through the opening 116d).

Here, the supply gas flow path member 124 and the permeate gas flow path member 126 constitute a gas flow path and function as a spacer between the module laminates 114. For example, a net shape (mesh Member).
The telescope prevention plate 116 includes an annular outer ring part 116a, an annular inner ring part 116b arranged in the outer ring part 116a so as to coincide with the center, an outer ring part 116a and an inner ring part. Ribs (spokes) 116c for connecting and fixing 116b, and the gaps between the ribs 116c are openings 116d through which the source gas G or the residual gas Gr passes.

  As mentioned above, although the manufacturing method of the laminated body for acidic gas separation of this invention was demonstrated in detail, this invention is not limited to the above-mentioned example, In the range which does not deviate from the summary of this invention, various improvement and change are performed. Of course, you may.

  Hereinafter, the specific example of this invention is given and the manufacturing method of the laminated body for acidic gas separation of this invention is demonstrated in detail.

[Example 1]
<Silicone coating solution>
UV9300 made by Momentive Performance Materials was prepared as a silicone coating solution for forming the silicone resin layer. Further, 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate manufactured by Tokyo Chemical Industry Co., Ltd. was added as a curing agent in an amount of 0.5% by weight based on the silicone coating solution. Further, as the filler, a material: silica, an average particle diameter: 0.01 μm, and a shape: a spherical filler were added so as to have a particle concentration of 4 wt%.

<Support>
A support roll 12R obtained by winding a long (porous) support 12 having a width of 500 mm and a thickness of 200 μm in a roll shape was prepared. In addition, the support body 12 used the laminated body (made by GE) which laminated | stacked porous PTFE as the porous membrane 12a on the surface of PP nonwoven fabric as the auxiliary support membrane 12b.

<Preparation of composite 18>
In the RtoR manufacturing apparatus, a silicone coating solution was applied to the porous membrane 12a side and cured to produce a composite 18 in which the silicone resin layer 14 was formed on the surface of the porous support 12. The film thickness of the silicone resin layer 14 was 2 μm.
The ratio of the protrusions on the surface of the silicone resin layer 14 was measured with an SEM (SU3500, manufactured by Hitachi High-Tech) at a scanning magnification of 10,000 times, and on the SEM image in the range of 9 μm × 12 μm, the diameter was 100 nm. The ratio of the number of the above protrusions was determined. The average value measured at 100 locations was 10 / μm ² .

<Coating composition of acid gas separation layer 16>
As a coating composition for forming the acidic gas separation layer 16, 2.4% by mass of a polyvinyl alcohol-polyacrylic acid copolymer (Kuraray Co., Ltd., Clastomer AP-20) and a crosslinking agent (Wako Pure Chemical Industries, Ltd., 25% by mass) are used. An aqueous solution containing 0.01% by mass of a 1% glutaraldehyde aqueous solution) was prepared. To this aqueous solution, 1M hydrochloric acid was added until the pH reached 1.5 to cause crosslinking.
After crosslinking, a 40% aqueous cesium carbonate solution (manufactured by Rare Metal Co., Ltd.) and an aqueous potassium carbonate solution (manufactured by Wako Pure Chemical Industries, Ltd.) as the carrier are each cesium carbonate concentration of 5 mass% and potassium carbonate concentration of 1 mass%. It added so that it might become. That is, in this example, cesium carbonate and potassium carbonate are carriers of the acidic gas separation layer 16. Further, a surfactant was added so that the surface tension of the coating composition was 30 mN / m.

<Production of Acid Gas Separation Laminate 10>
In the manufacturing apparatus 50 shown in FIG. 2, the coating composition is applied to the surface of the composite 18 on the silicone resin layer 14 side and dried to form the acidic gas separation layer 16 having a thickness of 30 μm. The laminated body 10 for acidic gas separation which consists of the acidic gas separation layer 16 and the composite_body | complex 18 was produced.
The conveyance speed of the composite 18 was 3 m / min. The viscosity of the coating composition at 25 ° C. was 1100 cp. Viscosity was measured according to JIS Z8803 using a TVB-10M manufactured by Toki Sangyo Co., Ltd., which is a B viscometer, and the rotor was spindle No. The value 30 seconds after the start of rotation was measured as the viscosity of the silicone coating solution at M4 and a rotation speed of 60 rpm.

[Example 2]
A laminate for acidic gas separation was produced in the same manner as in Example 1 except that the addition amount of the surfactant was changed and the surface tension of the coating composition was changed to 65 mN / m.

[Example 3]
A laminate for acidic gas separation was produced in the same manner as in Example 1 except that the amount of pure water added was changed and the viscosity of the coating composition was 80 cp.

[Example 4]
Example except that the filler concentration in the silicone resin layer was 6 wt%, and that the surface of the formed silicone resin layer 14 was subjected to plasma treatment so that the ratio of protrusions on the surface of the silicone resin layer was 50 / μm ^2. In the same manner as in Example 1, an acid gas separation laminate was produced.

[Comparative Example 1]
A laminate for acidic gas separation was produced in the same manner as in Example 1 except that the filler was not dispersed in the silicone resin layer.
Before forming the acidic gas separation layer 16, the ratio of the protrusions on the surface of the silicone resin layer was measured by the same method as in Example 1. As a result, the ratio of the protrusions on the surface was 0.01 pieces / μm ^2. It was.

[Comparative Example 2]
A laminated body for acid gas separation was produced in the same manner as in Example 1 except that the particle concentration of the filler in the silicone resin layer was 80 wt% and the ratio of protrusions on the surface of the silicone resin layer was 70 / μm ² . .

[Evaluation]
Evaluation was performed by measuring the film thickness variation, peel force, and presence / absence of film defects of the laminate for acidic gas separation produced in each comparative example.

<Thickness variation test>
The acidic gas separation layer was dried by leaving the acidic gas separation layer for 24 hours in an environment of 30% humidity and a temperature of 25 ° C. for the produced laminated body for acidic gas separation. Thereafter, the laminate was put into liquid nitrogen and cut with a knife to obtain a cross section. Next, the SEM image of the cross section was acquired and the film thickness of the acidic gas separation layer was calculated. The film thickness was measured at a total of 9 points, 3 points in the TD direction (flow direction) and 3 points in the MD direction (vertical direction), and the variation in film thickness of the acid gas separation layer was measured. The film thickness variation was the maximum value of the ratio of the difference with respect to the average value of 9 points.
The evaluation criteria were A for a film thickness variation of 30% or less, B for more than 30% and 50% or less, and C for more than 50%.

<Peeling force test (peel test)>
A 50 mm × 8 mm sample piece was prepared from the produced laminate for acidic gas separation, and the peel force between the acidic gas separation layer and the silicone resin layer was measured using a peel tester (manufactured by Imada Co., Ltd.).
The evaluation criteria were A when the peel force was greater than 0.07N and B when it was 0.07N or less.

<Film defect evaluation>
The presence / absence of a film defect in the produced laminate for acidic gas separation 10 was evaluated by measuring gas permeability at a plurality of locations of the laminate 10.
Specifically, each produced acid gas separation laminate 10 was pulled out from the laminate roll 10R and cut out at an arbitrary position to produce a circular acid gas separation laminate sample (hereinafter referred to as a sample) having a diameter of 47 mm. . In addition, the circular sample was cut out at a total of 6 locations, 3 locations in the TD direction and 2 locations in the MD direction, to produce 6 samples.
Using two PTFE membrane filters (pore size 0.10 μm, manufactured by ADVANTEC), a cut-out circular sample was sandwiched from both sides of the membrane to prepare a transmission test sample (effective area 2.40 cm 2).
A mixed gas of CO ₂ / H ₂ : 10/90 (volume ratio) was used as a test gas. This mixed gas was supplied to each prepared sample under the conditions of a relative humidity of 70%, a flow rate of 100 mL / min, a temperature of 130 ° C., and a total pressure of 3 atm. Ar gas (flow rate 90 mL / min) was allowed to flow on the permeate side.
The permeated gas was analyzed with a gas chromatograph, and the separation factor α was calculated from the ratio of the H ₂ permeation rate and the CO ₂ permeation rate, and evaluated as follows.
A: α ≧ 80 at all six locations.
B: 10 <α <80 is included even at one place.
C: α ≦ 10 is included even at one location.
The results are shown in the table below.

As shown in the above table, the acid gas separation laminate 10 produced by the production method of the present invention has a small film thickness variation and a high evaluation of film defects. It can be seen that the repelling at the time of coating can be suppressed, and the coating composition can be properly coated. Moreover, it turns out that it is excellent also in the adhesiveness of an acidic gas separation layer and a silicone resin layer. Therefore, it turns out that an acidic gas separation layer with high durability can be manufactured suitably. In addition, the acidic gas separation layer can be prevented from entering the porous support, and the acid gas separation layer has small film thickness variation and high evaluation of membrane defects, so that the acid gas permeability and separation properties are excellent. I understand that.
On the other hand, in Comparative Example 1 in which the ratio of the protrusions on the surface of the silicone resin layer is less than 0.1 / μm ² , since the film thickness variation is large, the coating composition for the acidic gas separation layer is applied at the time of manufacture. It can be seen that the repelling at the time is large and the coating composition cannot be applied properly. Moreover, it turns out that the adhesiveness of an acidic gas separation layer and a silicone resin layer is also low, and durability is low.
On the other hand, in Comparative Example 2 in which the ratio of protrusions on the surface of the silicone resin layer exceeds 50 pieces / μm ² , the ratio of protrusions is too large, so that the film thickness variation is large and film defects are likely to occur. .

Further, from the comparison between Examples 1 and 2, it can be seen that the surface tension of the coating composition is preferably 63 mN / m or less.
Further, from the comparison of Examples 1 and 3, it is understood that the viscosity of the coating composition is preferably 100 cp or more.
In addition, it can be seen from Example 4 that even when the proportion of protrusions is increased by combining filler inclusion and plasma treatment, film defects can be made difficult to occur.
From the above results, the effects of the present invention are clear.

  It can be suitably used for an acid gas separation laminate used for hydrogen gas production, natural gas purification, and the like.

10 acidic gas separation laminate 10R laminate roll 12 (porous) support 12R support roll 12a porous membrane 12b auxiliary support membrane 14 silicone resin layer 16 acidic gas separation layer 18 composite 18R composite roll 20, 50 production Device 24, 52 Supply unit 26, 54 Coating unit 28 Curing device 30, 58 Winding unit 31, 61 Rotating shaft 32, 62 Coating device 34, 64 Backup roller 38a-38e, 68a-68e Pass roller 40, 70 Winding shaft 56 Dryer 100 Acid gas separation module 112 Center tube 112a Through hole 112b Open end 114 Module stack 116 Telescope prevention plate 116a Outer ring part 116b Inner ring part 116c Rib 116d Opening part 118 Covering layer 124 Supply gas channel member 126 Permeating gas channel member 13 Adhesive layer

Claims (10)

An acidic gas comprising a composite provided with a silicone resin layer on at least a part of the surface of a porous support, a carrier that reacts with an acidic gas, and a water-absorbing polymer that carries the carrier, formed on the silicone resin layer A method for producing a laminate for acidic gas separation comprising a separation layer,
A separation layer forming step of forming the acidic gas separation layer on the silicone resin layer of the composite;
The ratio of protrusions having a diameter of 100 nm or more measured by a scanning electron microscope on the surface of the silicone resin layer of the composite to be subjected to the separation layer forming step is 0.1 / μm ² to 50. / Μm ^{2 The} method for producing a laminate for separating acidic gas, wherein   The method for producing a laminate for acidic gas separation according to claim 1, wherein the water-absorbing polymer is a polyvinyl alcohol-polyacrylic acid copolymer.   The manufacturing method of the laminated body for acidic gas separation of Claim 1 or 2 in which the said carrier contains the compound containing alkali metal carbonate.   The method for producing a laminate for acidic gas separation according to any one of claims 1 to 3, wherein the silicone resin layer has a thickness of 10 µm or less. The acidity according to any one of claims 1 to 4, wherein the silicone resin layer includes a filler so that a ratio of protrusions on the surface is 0.1 / μm ² to 50 / μm ^2. A method for producing a laminate for gas separation.   The said separation layer formation process apply | coats the coating composition used as the said acidic gas separation layer to the surface of the said silicone resin layer by the roll-to-roll system, The acid of any one of Claims 1-5 A method for producing a laminate for gas separation.   The manufacturing method of the laminated body for acidic gas separation of Claim 6 whose surface tension of the said coating composition is 63 mN / m or less.   The method for producing a laminate for acidic gas separation according to claim 6 or 7, wherein the viscosity of the coating composition at 25 ° C is 100 cp or more. An acidic gas comprising a composite provided with a silicone resin layer on at least a part of the surface of a porous support, a carrier that reacts with an acidic gas, and a water-absorbing polymer that carries the carrier, formed on the silicone resin layer A laminate for acid gas separation comprising a separation layer,
A laminate for acidic gas separation, wherein a ratio of protrusions at an interface between the silicone resin layer and the acidic gas separation layer is 0.1 / μm ² to 50 / μm ² .   The acidic gas separation module which has the laminated body for acidic gas separation of Claim 9.

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